U.S. patent application number 17/092218 was filed with the patent office on 2022-04-14 for laser scanning ablation synthesis of medium-entropy and high-entropy particles with size from nanometer to micrometer.
This patent application is currently assigned to Nanjing University. The applicant listed for this patent is NANJING UNIVERSITY. Invention is credited to Bing WANG, Congping WU, Yingfang YAO, Zhigang Zou.
Application Number | 20220111466 17/092218 |
Document ID | / |
Family ID | |
Filed Date | 2022-04-14 |
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United States Patent
Application |
20220111466 |
Kind Code |
A1 |
Zou; Zhigang ; et
al. |
April 14, 2022 |
Laser scanning ablation synthesis of medium-entropy and
high-entropy particles with size from nanometer to micrometer
Abstract
A method for scaled-up synthesis of medium-entropy and
high-entropy nanoparticles (NPs) including alloys and ceramics on
various substrates such as carbon, metal and glass. The method
requires only two steps to synthesize these NPs, including loading
metal salt precursors with equal molar ratio onto a support and
irradiating the support by highly intense laser pulses in liquid at
ambient atmosphere. The method ensures multiple (3.about.9) atoms
to combine without segregation regardless of their mutual
solubility. The method can easily tailor the particle size from
nanometer to micrometer by controlling the parameters.
Inventors: |
Zou; Zhigang; (Nanjing,
CN) ; WANG; Bing; (Nanjing, CN) ; YAO;
Yingfang; (Nanjing, CN) ; WU; Congping;
(Nanjing, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NANJING UNIVERSITY |
Nanjing |
|
CN |
|
|
Assignee: |
Nanjing University
Nanjing
CN
|
Appl. No.: |
17/092218 |
Filed: |
November 7, 2020 |
International
Class: |
B23K 26/361 20060101
B23K026/361; B23K 26/082 20060101 B23K026/082; B23K 26/402 20060101
B23K026/402 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 14, 2020 |
CN |
202011094113.4 |
Claims
1. A laser scanning ablation method of synthesizing medium-entropy
and high-entropy nanoparticles (NPs), comprising: step (1)
dissolving precursors of each element in medium-entropy or
high-entropy NPs in solvent with equal molar ratio or near equal
molar ratio to form a solution, and then dripping the solution onto
a substrate and dried. step (2) transferring the substrate in step
(1) to a beaker, and irradiated under laser pulse in a liquid
phase.
2. According to the laser scanning ablation method of synthesizing
medium-entropy and high-entropy NPs mentioned in claim 1, wherein
medium-entropy or high entropy NPs involved in step (1) include
alloys, oxides, sulfides, phosphides, carbides, nitrides and
borides.
3. According to the laser scanning ablation method of synthesizing
medium-entropy and high-entropy NPs mentioned in claim 1, wherein
the elements of medium-entropy or high-entropy NPs involved in step
(1) include platinum, gold, palladium, iridium, ruthenium, rhodium,
cesium, copper, chromium, tin, iron, cobalt, nickel, zinc,
manganese, vanadium, tantalum, tungsten, rhenium, osmium, hafnium,
indium, rubidium, strontium, sulfur, carbon, nitrogen, oxygen,
phosphorus, boron, lithium; and the precursors of each element
involved in step (1) include chloride, sulfate, phosphate, nitrate
and sulfur powder, phosphorus powder, sodium hypophosphate, sodium
borate and hydroxide.
4. According to the laser scanning ablation of synthesizing
medium-entropy and high-entropy NPs mentioned in claim 1, wherein
the solvent involved in step (1) includes ethanol, methanol, water,
acetone, isopropyl alcohol, and carbon disulfide.
5. According to the laser scanning ablation of synthesizing
medium-entropy and high-entropy NPs mentioned in claim 1, wherein
the substrate involved in step (1) includes carbon, metal, organic
and inorganic materials.
6. According to the laser scanning ablation of synthesizing
medium-entropy and high-entropy NPs mentioned in claim 1, wherein
the liquid phase environment involved in step (2) includes all
kinds of alkanes, ethanol, water, methanol, etc.
7. According to the laser scanning ablation of synthesizing
medium-entropy and high-entropy NPs mentioned in claim 1, wherein
the laser pulse involved in step (2) includes nanosecond lasers and
femtosecond lasers.
8. According to the laser scanning ablation of synthesizing
medium-entropy and high-entropy NPs mentioned in claim 1, wherein
the parameters of the laser involved in step (2) are the power
density of 10.sup.5.about.10.sup.9 W/cm.sup.2 and the frequency of
1 Hz.about.80 kHz; and the wavelength range of the laser covers
ultraviolet, visible and infrared light.
Description
BACKGROUND
Field of Invention
[0001] The present disclosure relates to nanotechnology, and
particularly to a method of synthesizing medium-entropy and
high-entropy nanoparticles (NPs) using laser scanning ablation.
Description of Related Art
[0002] Medium-entropy and high-entropy NPs including alloy NPs and
ceramics NPs have attracted considerable attention due to its
unique configuration and promising properties such as high
strength, unique electrical and magnetic properties, and promising
resistances to wear, oxidation and corrosion. The controllable
synthesis of medium-entropy and high-entropy NPs has tremendous
application merits in many fields such as thermoelectricity,
dielectric, catalysis, and energy storage, yet remains a challenge
due to the lack of robust strategies. Synthesis of these NPs has
been achieved by a few methods such as carbothermal shock and
moving bed pyrolysis. However, these techniques only produce HEA
NP, but not HEC NP. They require inert atmosphere and high
temperature which are only applied to thermally-resistant
substrates rather than thermally-sensitive substrates. Thus, a
method of synthesizing medium-entropy and high-entropy NPs with
broad substrate applicability under mild conditions is desired.
SUMMARY OF THE INVENTION
[0003] A laser scanning ablation (LSA) method of synthesizing
medium-entropy and high-entropy NPs includes loading metal salt
precursors with equal molar ratio onto a support and irradiating
the support by highly intense laser pulses in liquid at ambient
atmosphere.
[0004] The LSA method allows the synthesis of impurity-free
medium-entropy and high-entropy NPs with thermodynamically
forbidden composition and uniform elemental distributions. The size
of particles within a range from several nanometers to micrometers
can be kinetically controlled by the ablation parameters as well as
liquid temperature. The method allows medium-entropy and
high-entropy NPs loaded onto various substrates such as carbon
materials, glass and metals. The LSA method of synthesizing
medium-entropy and high-entropy NPs has the advantages of simple
operation, low cost, mild reaction condition, high efficiency and
environmental protection.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 An SEM image of (AuFeCoCuCr) HEA-NPs loaded on carbon
nanofibers (CNFs) prepared in Example 1 with the scale bar of 100
nm. A TEM image of a AuFeCoCuCr HEA NP with the scale bar of 20 nm
and the corresponding Energy-dispersive X-ray spectroscopy (EDS)
maps of Au, Fe, Co, Cu, Cr elements.
[0006] FIG. 2 A TEM image of (PtAuPdCuCrSnFeCoNi) HEA-NPs prepared
in Example 2 and the EDS maps of Pt, Au, Pd, Cu, Cr, Sn, Fe, Co, Ni
elements. Scale bar, 20 nm.
[0007] FIG. 3 XRD pattern of novenary (PtAuPdCuCrSnFeCoNi) HEA-NPs
prepared in Example 2.
[0008] FIG. 4 An SEM of (PtAuPdFeCo) HEA NPs on carbonized wood
prepared in Example 3 with the scale bar of 100 .mu.m and the EDS
maps of Pt, Au, Pd, Fe, Co elements with the scale bar of 1
.mu.m.
[0009] FIG. 5 A TEM image of (PtIrCuNiCr) HEA NPs on graphene
prepared in Example 4 with the scale bar of 50 nm and the EDS maps
of Pt, Ir, Cu, Ni, Cr elements with the scale bar of 10 nm.
[0010] FIG. 6 An LSV curve of two-electrode cell assembled by
bifunctional PtIrCuNiCr-graphene electrocatalysts as both cathode
and anode.
[0011] FIG. 7 An SEM of (PtAuFeCoNi) HEA NPs on copper foam
prepared in Example 5 with the scale bar of 10 .mu.m and the EDS
maps of Pt, Au, Fe, Co, Ni elements with the scale bar of 0.5
.mu.m.
[0012] FIG. 8 An SEM of (AuPdCuSnZn) HEA NPs on glass prepared in
Example 6 with the scale bar of 1 .mu.m and the EDS maps of Au, Pd,
Cu, Sn, Zn elements with the scale bar of 100 nm.
[0013] FIG. 9 An SEM of (CuCrFeCoNiS) HEC NPs on CNFs prepared in
Example 7 with the scale bar of 100 nm and the EDS maps of Cu, Cr,
Fe, Co, Ni, S elements with the scale bar of 50 nm.
[0014] FIG. 10 An SEM of (CuCrFeCoNiO) HEC NPs on CNFs prepared in
Example 8 with the scale bar of 100 nm and the EDS maps of Cu, Cr,
Fe, Co, Ni, O elements with the scale bar of 50 nm.
[0015] FIG. 11 A TEM image of medium-alloy PtAuCu NPs on carbon
nanofibers prepared in Example 9 with the scale bar of 200 nm and
the EDS maps of Pt, Au, Cu elements with the scale bar of 100
nm.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0016] Exemplary embodiments relate to a method of synthesizing
medium-entropy and high-entropy nanoparticles. Preferred
embodiments are described in detail below.
Example 1
[0017] The present patent discloses a laser ablation method of
synthesizing medium-entropy and high-entropy NPs, which includes
the following steps:
[0018] (1) Chloroauric acid, ferric chloride, cobalt chloride,
copper chloride and chromium chloride were dissolved in ethanol
with 0.01 M for each metallic element. The mixed solution was
directly dropped onto the carbon nanofiber prepared by
electrostatic spinning with a loading of .about.1 ml/cm.sup.2. Then
the loaded substrates were transferred to a vacuum oven for
drying.
[0019] (2) The carbon nanofiber in step (1) was transferred to a
beaker containing hexane (the liquid level was about 1 cm from the
bottom of the beaker), and a nanosecond pulse laser with a pulse
width of 5 ns was used to scan the surface of the carbon nanofiber.
The average laser power density was 2.times.10.sup.5 W/cm.sup.2 and
the frequency was 20 kHz.
[0020] As shown in the micrographs of FIG. 1, the elements of gold,
iron, cobalt, copper and chromium are uniformly dispersed among the
high-entropy alloy NPs synthesized from Example 1, while the alloy
particles are uniformly distributed on the surface of carbon
nanofiber. The average particle size of the high-entropy alloy NPs
synthesized in Example 1 is about 70 nm.
Example 2
[0021] Example 2 differs from Example 1 in that it includes the
following steps:
[0022] (1) Chloroplatinic acid, chloroauric acid, palladium
chloride, nickel chloride, ferric chloride, cobalt chloride, copper
chloride, chromium chloride, and tin chloride were dissolved in
ethanol with 0.01 M for each metallic element. The mixed solution
was directly dropped onto the carbon nanofiber prepared by
electrostatic spinning with a loading of .about.1 ml/cm.sup.2. Then
the loaded substrates were transferred to a vacuum oven for
drying.
[0023] (2) The carbon nanofiber in step (1) was transferred to a
beaker containing hexane (the liquid level was about 1 cm from the
bottom of the beaker), and a nanosecond pulse laser with a pulse
width of 5 ns was used to scan the surface of the carbon nanofiber.
The average laser power density was 2.times.10.sup.5 W/cm.sup.2 and
the frequency was 20 kHz.
[0024] As shown in the micrographs of FIG. 2, the elements of
platinum, gold, palladium, iron, cobalt, nickel, copper, chromium,
tin are uniformly dispersed among the high-entropy alloy NPs
synthesized from Example 2. The average particle size of the
high-entropy alloy NPs synthesized in Example 2 is about 50 nm.
[0025] As shown in the XRD pattern of FIG. 3, the high entropy
alloy NPs synthesized in Example 2 were assigned to face-centered
cubic structure.
Example 3
[0026] Example 3 differs from Example 1 and 2 in that it includes
the following steps:
[0027] (1) Chloroplatinic acid, chloroauric acid, palladium
chloride, ferric chloride, and cobalt chloride were dissolved in
ethanol with 0.01 M for each metallic element. The mixed solution
was directly dropped onto a carbonized block
(length.times.width.times.height=3 cm.times.3 cm.times.0.4 cm) with
a loading of .about.1 ml/cm.sup.2. Then the loaded block was
transferred to a vacuum oven for drying.
[0028] (2) The block in step (1) was transferred to a beaker
containing hexane (the liquid level was about 1 cm from the bottom
of the beaker), and a nanosecond pulse laser with a pulse width of
5 ns was used to scan the surface of the block. The average laser
power density was 2.times.10.sup.5 W/cm.sup.2 and the frequency was
30 kHz.
[0029] As shown in the micrographs of FIG. 4, the elements of
platinum, gold, palladium, iron and cobalt are uniformly dispersed
among the high-entropy alloy particles synthesized from Example 3,
while the alloy particles are uniformly distributed on the surface
of block. The average particle size of the high-entropy alloy NPs
synthesized in Example 3 is about 2.about.3 micrometer.
EXAMPLE
[0030] Example 4 differs from Example 1, 2 and 3 in that it
includes the following steps:
[0031] (1) Chloroplatinic acid, iridium chloride, copper chloride,
nickel chloride, and chromium chloride were dissolved in ethanol
with 0.01 M for each metallic element. The mixed solution was
directly dropped onto graphene with a loading of .about.0.1 ml/mg.
Then the loaded graphene was transferred to a vacuum oven for
drying.
[0032] (2) The precursors-loaded graphene was transferred in a
baker containing hexane. Then the solution was irradiated under
agitation with the laser for 30 min. The average laser power
density was 2.times.10.sup.5 W/cm.sup.2 and the frequency was 30
kHz.
[0033] As shown in the micrographs of FIG. 5, the elements of
platinum, iridium, copper, nickel, chromium are uniformly dispersed
among the high-entropy alloy NPs synthesized from Example 4, while
the alloy particles are uniformly distributed on graphene. The
average particle size of the high-entropy alloy NPs synthesized in
Example 4 is about 5 nanometers.
[0034] As shown in the electrocatalytic water splitting diagram of
FIG. 6, the high entropy alloy NPs synthesized in Example 4 has
excellent electrocatalytic activity as bifunctional
electrocatalysts.
Example 5
[0035] Example 5 differs from Example 1, 2, 3 and 4 in that it
includes the following steps:
[0036] (1) Chloroplatinic acid, chloroauric acid, nickel chloride,
ferric chloride, and cobalt chloride were dissolved in ethanol with
0.01 M for each metallic element. The mixed solution was directly
dropped onto a copper foam with a loading of .about.1 ml/cm.sup.2.
Then the loaded substrates were transferred to a vacuum oven for
drying.
[0037] (2) The copper foam in step (1) was transferred to a beaker
containing hexane (the liquid level was about 1 cm from the bottom
of the beaker), and a nanosecond pulse laser with a pulse width of
5 ns was used to scan the surface of the copper foam. The average
laser power density was 2.times.10.sup.5 W/cm.sup.2 and the
frequency was 20 kHz.
[0038] As shown in the micrographs of FIG. 7, the elements of
platinum, gold, iron, cobalt, nickel are uniformly dispersed among
the high-entropy alloy NPs synthesized from Example 5, while the
alloy particles are uniformly distributed on the surface of carbon
nanofiber. The average particle size of the high-entropy alloy NPs
synthesized in Example 5 is about 700 nm.
Example 6
[0039] Example 6 differs from Example 1, 2, 3, 4 and 5 in that it
includes the following steps:
[0040] (1) Chloroauric acid, palladium chloride, zinc chloride,
copper chloride, and tin chloride were dissolved in ethanol with
0.01 M for each metallic element. The mixed solution was directly
dropped onto a glass slide with a loading of .about.1 ml/cm.sup.2.
Then the loaded substrates were transferred to a vacuum oven for
drying.
[0041] (2) The glass slide in step (1) was transferred to a beaker
containing hexane (the liquid level was about 1 cm from the bottom
of the beaker), and a nanosecond pulse laser with a pulse width of
5 ns was used to scan the surface of the glass slide. The average
laser power density was 2.times.10.sup.5 W/cm.sup.2 and the
frequency was 10 kHz.
[0042] As shown in the micrographs of FIG. 8, the elements of gold,
palladium, copper, tin, zinc are uniformly dispersed among the
high-entropy alloy NPs synthesized from Example 6, while the alloy
particles are uniformly distributed on the surface of carbon
nanofiber. The average particle size of the high-entropy alloy NPs
synthesized in Example 6 is about 120 nm.
Example 7
[0043] Example 7 differs from Example 1, 2, 3, 4, 5 and 6 in that
it includes the following steps:
[0044] (1) Copper chloride, chromium chloride, ferric chloride,
cobalt chloride, and nickel chloride were dissolved in ethanol with
0.01 M for each metallic element. The mixed solution was directly
dropped onto a carbon nanofiber with a loading of .about.1
ml/cm.sup.2. Then the carbon disulfide solution dissolved in 0.05M
sulfur powder was dripped on the carbon nanofiber at a dose of 1
ml/cm.sup.2. The loaded substrates were transferred to a vacuum
oven for drying.
[0045] (2) The carbon nanofiber in step (1) was transferred to a
beaker containing hexane (the liquid level was about 1 cm from the
bottom of the beaker), and a nanosecond pulse laser with a pulse
width of 5 ns was used to scan the surface of the carbon nanofiber.
The average laser power density was 2.times.10.sup.5 W/cm.sup.2 and
the frequency was 10 kHz.
[0046] As shown in the micrographs of FIG. 9, the elements of
copper, chromium, iron, cobalt, nickel, sulfur are uniformly
dispersed among the high-entropy alloy NPs synthesized from Example
7, while the alloy particles are uniformly distributed on the
surface of carbon nanofiber.
Example 8
[0047] Example 8 differs from Example 1, 2, 3, 4, 5, 6 and 7 in
that it includes the following steps:
[0048] (1) Copper chloride, chromium chloride, ferric chloride,
cobalt chloride, and nickel chloride were dissolved in ethanol with
0.01 M for each metallic element. The mixed solution was directly
dropped onto a carbon nanofiber with a loading of .about.1
ml/cm.sup.2. Then the sodium hydroxide aqueous solution of 0.05M
was dripped on the carbon fiber at a dose of 1 ml/cm.sup.2. The
loaded substrates were transferred to a vacuum oven for drying.
[0049] (2) The carbon nanofiber in step (1) was transferred to a
beaker containing hexane (the liquid level was about 1 cm from the
bottom of the beaker), and a nanosecond pulse laser with a pulse
width of 5 ns was used to scan the surface of the carbon nanofiber.
The average laser power density was 2.times.10.sup.5 W/cm.sup.2 and
the frequency was 10 kHz.
[0050] As shown in the micrographs of FIG. 10, the elements of
copper, chromium, iron, cobalt, nickel, and sulfur are uniformly
dispersed among the high-entropy alloy NPs synthesized from Example
8, while the alloy particles are uniformly distributed on the
surface of carbon nanofiber.
Example 9
[0051] Example 9 differs from Example 1, 2, 3, 4, 5, 6, 7 and 8 in
that it includes the following steps:
[0052] (1) Chloroplatinic acid, chloroauric acid, copper chloride
were dissolved in ethanol with 0.01 M for each metallic element.
The mixed solution was directly dropped onto a carbon nanofiber
with a loading of .about.1 ml/cm.sup.2. The loaded substrates were
transferred to a vacuum oven for drying.
[0053] (2) The carbon nanofiber in step (1) was transferred to a
beaker containing hexane (the liquid level was about 1 cm from the
bottom of the beaker), and a nanosecond pulse laser with a pulse
width of 5 ns was used to scan the surface of the carbon nanofiber.
The average laser power density was 2.times.10.sup.5 W/cm.sup.2 and
the frequency was 10 kHz.
[0054] As shown in the micrographs of FIG. 11, the elements of
platinum, gold and copper are uniformly dispersed among the
medium-entropy alloy NPs synthesized from Example 9.
* * * * *